JP2020002237A - Detergent composition for substrate for semiconductor device - Google Patents

Abstract

To provide a detergent composition for a substrate for a semiconductor device excellent in cleaning properties to ceria remained on a substrate surface, a method of cleaning a substrate for semiconductor device using the detergent composition, and a method of manufacturing a substrate for semiconductor device.SOLUTION: The detergent composition for a substrate for a semiconductor device includes: a polymer (a constituent A) including a constitutional unit a1 derived from a vinyl-based monomer a1 having a carbonic acid group or an anhydride thereof, a constitutional unit a2 derived from a vinyl-based monomer a2 having a phosphoric acid group and a carbonic acid group, and a constitutional unit a3 derived from a vinyl-based monomer a3 having two carbonic acid groups through a phosphoric acid group; sulfuric acid (a constituent B); and water (a constituent C).SELECTED DRAWING: None

Description

  The present disclosure relates to a cleaning composition for a semiconductor device substrate, a method for cleaning a semiconductor device substrate using the cleaning composition, and a method for manufacturing a semiconductor device substrate.

  2. Description of the Related Art In recent years, semiconductor devices such as semiconductor integrated circuits have been miniaturized with the improvement in processing capability. As the miniaturization progresses, high accuracy of flatness in each layer of the substrate is required. Furthermore, it has been required from the viewpoint of production efficiency and the like to simultaneously planarize a plurality of types of surfaces having different hardnesses and properties on which wirings and the like are drawn.

Chemical mechanical polishing (CMP) is generally performed as a technique for ensuring the flatness of a substrate for a semiconductor device. In CMP, a substrate surface is polished and flattened using a polishing pad while supplying an abrasive (slurry) containing abrasive grains. Silica slurry is widely used as an abrasive, but cerium oxide particle (ceria) slurry is also used. The silica slurry is mainly used for polishing a substrate surface having a metal portion such as copper and a silicon dioxide (SiO ₂ ) portion, and the ceria slurry mainly has a SiO ₂ portion and a silicon nitride (Si ₃ N ₄ ) portion. It is used for polishing the substrate surface. After the CMP using the silica slurry or the ceria slurry, cleaning is necessary to remove polishing debris and foreign matter (particles) derived from abrasive grains remaining on the substrate surface. As a cleaning composition and a cleaning method used for cleaning a substrate after CMP, for example, the following cleaning compositions and cleaning methods have been proposed.

  For example, Patent Literature 1 discloses a structural unit derived from a vinyl monomer having a carboxylic acid group and a structural unit derived from a vinyl monomer having a sulfonic acid group, which is excellent in detergency for ceria and dispersibility of ceria and silica. Polymer (Component A), Polymer other than Component A (Component B), Sulfuric Acid (Component C), Reducing Agent (Component D), and Water (Component E) Containing Structural Units Derived from Aromatic Monomers Having Sulfonic Acid Groups There has been proposed a cleaning composition for a substrate for a semiconductor device, comprising:

  Patent Document 2 discloses an ethylene oxide and propylene oxide adduct of a monoamine having 10 to 22 carbon atoms, which is excellent in cleaning properties for ceria and can suppress deterioration of the surface roughness of the substrate after cleaning, sulfuric acid, a reducing agent, and water. There has been proposed an acidic cleaning composition for a substrate for a semiconductor device, comprising:

  Patent Literature 3 discloses a method for removing contaminants caused by cerium oxide or manganese oxide on a substrate, in which a semiconductor substrate is subjected to chemical mechanical polishing, and then the substrate is made of a reducing agent and an acid. A method of cleaning a semiconductor substrate using a mixed solution has been proposed.

JP 2018-46153 A JP-A-2017-120844 JP-A-11-251280

  After the CMP using the ceria slurry, hydrofluoric acid cleaning is usually performed for the purpose of removing ceria, which is a polishing abrasive grain remaining on the substrate surface. On the other hand, in recent years, in the field of semiconductor devices, the wiring width has been narrowed for the purpose of miniaturization, and thus the influence of scratches and surface roughness of a thermal oxide film such as silicon dioxide forming the base has increased. Furthermore, hydrofluoric acid cleaning has problems such as scratch generation and surface roughness due to too high solubility in the thermal oxide film, which affects the post-cleaning process, and reduces the yield and quality of semiconductor devices. Inviting. Therefore, there has been a demand for a cleaning agent which is excellent in cleaning performance for ceria remaining on the substrate surface without lowering the flatness, instead of hydrofluoric acid. However, the cleaning compositions disclosed in the above-mentioned patent documents have insufficient cleaning properties for ceria remaining on the substrate surface.

  Therefore, the present disclosure provides a cleaning composition for a semiconductor device substrate having excellent cleaning properties for ceria remaining on a substrate surface, a method for cleaning a semiconductor device substrate using the cleaning composition, and a method for manufacturing a semiconductor device substrate. Provide a method.

〔式（Ｉ）中、Ｒ¹、Ｒ²及びＲ³はそれぞれ独立に、水素原子、メチル基、又は−(ＣＨ₂)_pＣＯＯＭ¹を示し、Ｒ⁴は、−（ＣＨ₂）_qＣＯＯ（ＡＯ）_n−Ｘ、又は−（ＣＨ₂）_rＯ（ＡＯ）_m−Ｙを示し、Ｍ¹は、水素原子、アルカリ金属、アルカリ土類金属（１／２原子）、有機アンモニウム基、又はアンモニウム基を示し、ｐ、ｑ及びｒはそれぞれ独立に、０以上２以下の整数を示し、ＡＯは炭素数２又は３のアルキレンオキシ基を示し、ｎ及びｍはそれぞれ独立に、ＡＯの平均付加モル数であって、４以上３００以下の数を示し、Ｘ及びＹはそれぞれ独立に、水素原子又は炭素数１以上３以下のアルキル基を示す。〕

〔式（ＩＩ）中、Ｒ⁵、Ｒ⁶及びＲ⁷はそれぞれ独立に、水素原子又はメチル基を示し、Ｒ⁸は炭素数２以上４以下のアルキレン基を示し、Ｍ²は、水素原子、アルカリ金属、アルカリ土類金属（１／２原子）、有機アンモニウム基、又はアンモニウム基を示す。〕

〔式（ＩＩＩ）中、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶はそれぞれ独立に、水素原子又はメチル基を示し、Ｒ¹²及びＲ¹³は炭素数２以上４以下のアルキレン基を示し、Ｍ³は、水素原子、アルカリ金属、アルカリ土類金属（１／２原子）、有機アンモニウム基、又はアンモニウム基を示す。〕 In one embodiment, the present disclosure relates to a monomer a1 represented by the following formula (I) or a structural unit a1 derived from an anhydride thereof, a structural unit a2 derived from a monomer a2 represented by the following formula (II), and a compound represented by the following formula (III) The present invention relates to a cleaning composition for a substrate for a semiconductor device, comprising a polymer containing a structural unit a3 derived from a monomer a3 (component A), sulfuric acid (component B), and water (component C).

[In the formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group, or — (CH ₂ ) _p COOM ¹ , and R ⁴ represents — (CH ₂ ) _q COO ( AO) _n -X or-(CH ₂ ) _r O (AO) _m -Y, and M ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or ammonium P, q and r each independently represent an integer of 0 or more and 2 or less; AO represents an alkyleneoxy group having 2 or 3 carbon atoms; n and m each independently represent an average addition mole of AO X and Y each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

[In the formula (II), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, R ⁸ represents an alkylene group having 2 to 4 carbon atoms, M ² represents a hydrogen atom, It represents an alkali metal, an alkaline earth metal (原子 atom), an organic ammonium group, or an ammonium group. ]

[In the formula (III), R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, and R ¹² and R ^{13 each} have 2 to 4 carbon atoms. M ³ represents a hydrogen atom, an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group. ]

  The present disclosure includes, in one embodiment, a step of cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure, wherein the substrate to be cleaned is a substrate used for manufacturing a substrate for a semiconductor device. A cleaning method.

  The present disclosure, in one aspect, relates to a method for manufacturing a substrate for a semiconductor device, including a step of cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure.

  According to the present disclosure, in one embodiment, it is possible to provide a cleaning composition for a substrate for a semiconductor device, which is excellent in cleaning properties for ceria remaining on a substrate surface.

  The present disclosure is based on the finding that ceria remaining on a substrate surface can be efficiently cleaned by using a cleaning composition containing the above components A to C for cleaning a substrate after CMP using a ceria slurry.

  That is, in one embodiment, the present disclosure relates to a monomer a1 represented by the above formula (I) or a structural unit a1 derived from an anhydride thereof, a structural unit a2 derived from a monomer a2 represented by the above formula (II), and the above formula A cleaning composition for a substrate for a semiconductor device, comprising a polymer (component A) containing a structural unit a3 derived from a monomer a3 represented by (III), sulfuric acid (component B), and water (component C). (Hereinafter, also referred to as “detergent composition according to the present disclosure”). ADVANTAGE OF THE INVENTION According to this indication, the cleaning composition for substrates for semiconductor devices which is excellent in the cleaning property with respect to the ceria which remains on a substrate surface can be provided. Then, by using the cleaning composition according to the present disclosure, a high-quality substrate for a semiconductor device can be obtained.

The details of the action mechanism of the effect of the cleaning composition according to the present disclosure are not clear, but are presumed as follows.
After the CMP using the ceria slurry, ceria, which is abrasive grains, remains on the substrate surface. When the ceria-adhered substrate is cleaned using the cleaning composition of the present disclosure, the component A having high dispersibility permeates between the substrate surface and the ceria and is adsorbed on the ceria surface, so that ceria is contained in the cleaning liquid composition. It is believed that the particles are dispersed and the substrate surface is cleaned. In particular, it is considered that since component A has monomer a2 and monomer a3 as constituent units, the adsorptivity to ceria is improved, and thus the detergency is improved. Further, the ceria particles to which the component A has been adsorbed, since the component A has the monomer a1 as a constituent unit, the contact between the ceria particles and the contact between the ceria particles and the substrate surface are suppressed. It is considered that ceria particles are dispersed therein and can prevent reattachment to the substrate surface. When the cleaning composition of the present disclosure further includes a reducing agent (component D), it is thought that the presence of component D can promote penetration of component A between the substrate surface and ceria, thereby improving cleaning properties. .
However, the present disclosure need not be construed as being limited to this mechanism.

[Component A: polymer]
The component A contained in the cleaning composition according to the present disclosure includes a monomer a1 represented by the following formula (I) or a structural unit a1 derived from an anhydride thereof, and a configuration derived from a monomer a2 represented by the following formula (II). It is a polymer containing a unit a2 and a structural unit a3 derived from a monomer a3 represented by the following formula (III). In the present disclosure, the component A can be used alone or in combination of two or more.

<Monomer a1>

In the formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group, or — (CH ₂ ) _p COOM ¹ , and R ⁴ represents — (CH ₂ ) _q COO (AO ) _n -X, or - (CH ₂₎ shows the _{r O (AO) m -Y,} M 1 is a hydrogen atom, an alkali metal, alkaline earth metal (1/2 atoms), an organic ammonium group, or an ammonium group And p, q and r each independently represent an integer of 0 or more and 2 or less, AO represents an alkyleneoxy group having 2 or 3 carbon atoms, n and m each independently represent the average number of moles of AO added Wherein X and Y each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In the formula (I), R ¹ , R ² and R ³ are each independently at least one kind selected from a hydrogen atom, a methyl group, or — (CH ₂ ) _p COOM ^{1, and} from the viewpoint of improving detergency. , R ¹ and R ³ is a hydrogen atom, R ² is preferably a hydrogen atom or a methyl group, R ¹ and R ³ is a hydrogen atom, R ² is more preferably a methyl group. R ⁴ is at least one selected from — (CH ₂ ) _q COO (AO) _n —X and — (CH ₂ ) _r O (AO) _m —Y. ⁴ _{- (CH 2) q COO (} AO) n -X is preferred.

  In the formula (I), p, q and r are each independently an integer of 0 or more and 2 or less, preferably 1 or less, more preferably 0, from the viewpoints of availability and improvement in cleaning properties.

  In the formula (I), AO represents an alkyleneoxy group having 2 or 3 carbon atoms, and the alkyleneoxy group may be in any of a linear or branched form. AO may be one kind or two or more kinds. When the number of AOs is two or more, the addition form may be random or block. The AO includes, for example, an oxyethylene (EO) group and an oxypropylene (PO) group, and an oxyethylene (EO) group is preferable from the viewpoint of improving detergency.

  In the formula (I), m and n each independently represent a number of 0 or more and 300 or less, and from the viewpoint of improving the cleaning property, 200 or less is preferable, 150 or less is more preferable, and 130 or less is further preferable.

In the formula (I), M ¹ represents a hydrogen atom, an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group. When M ¹ is a hydrogen atom, the monomer a1 is a carboxylic acid. When M ¹ is an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group, the monomer a1 is a salt of a carboxylic acid. M ¹ is preferably an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group, and more preferably an organic ammonium group or an ammonium group, from the viewpoint of improving cleanability.

  In the formula (I), X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of improving the cleaning properties. The alkyl group may be in any of a linear or branched form. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the same viewpoint, a methyl group is preferable.

  In the formula (I), Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of improving the cleaning properties. The alkyl group may be in any of a linear or branched form. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

In one embodiment of the monomer a1, R ¹ and R ³ in the formula (I) are a hydrogen atom, R ² is a hydrogen atom or a methyl group, and R ⁴ is — (CH ₂ ) _q COO (AO) _n − When X is 0 and q is 0, for example, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acryl At least one selected from acid esters, ethoxy polypropylene glycol (meth) acrylates, and propoxy polypropylene glycol (meth) acrylates, and methoxypolyethylene glycol (meth) acrylates from the viewpoint of improving detergency. , Ethoxypolyer At least one selected from lenglycol (meth) acrylate and propoxy polyethylene glycol (meth) acrylate is preferred, methoxypolyethylene glycol (meth) acrylate is more preferred, and methoxypolyethylene glycol methacrylate is even more preferred. preferable. “(Meth) acrylate” means at least one of acrylate and methacrylate.

In another embodiment of the monomer a1, R ^{1 to} R ³ in the formula (I) are hydrogen atoms, R ⁴ is — (CH ₂ ) _q COO (AO) _n —X, and q is 1 In this case, for example, methoxypolyethylene glycol-3-butenoate, ethoxypolyethyleneglycol-3-butenoate, propoxypolyethyleneglycol-3-butenoate, methoxypolypropyleneglycol-3-butenoate, ethoxypolypropyleneglycol-3- At least one selected from butenoic acid esters, propoxy polypropylene glycol-3-butenoic acid esters, and the like is included.

In another embodiment of the monomer a1, R ^{1 to} R ³ in the formula (I) are hydrogen atoms, R ⁴ is — (CH ₂ ) _q COO (AO) _n —X, and q is 2 In the case, for example, methoxypolyethylene glycol-4-pentenoate, ethoxypolyethyleneglycol-4-pentenoate, propoxypolyethyleneglycol-4-pentenoate, methoxypolypropyleneglycol-4-pentenoate, ethoxypolypropyleneglycol-4- At least one selected from pentenoic acid esters and propoxypolypropylene glycol-4-pentenoic acid esters is exemplified.

In another embodiment of the monomer a1, R ^{1 to} R ³ in the formula (I) are hydrogen atoms, R ⁴ is — (CH ₂ ) _r O (AO) _m —Y, and r is 0. In the case, for example, polyethylene glycol vinyl ether, methoxy polyethylene glycol vinyl ether, ethoxy polyethylene glycol vinyl ether, propoxy polyethylene glycol vinyl ether, polypropylene glycol vinyl ether, methoxy polypropylene glycol vinyl ether, ethoxy polypropylene glycol vinyl ether, propoxy polypropylene glycol vinyl ether, polyethylene glycol isopropenyl ether, and polypropane At least one selected from lenglycol isopropenyl ether and the like can be mentioned.

In another embodiment of the monomer a1, R ^{1 to} R ³ in the formula (I) are hydrogen atoms, R ⁴ is — (CH ₂ ) _r O (AO) _m —Y, and r is 1 In the case, for example, polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, ethoxy polyethylene glycol allyl ether, propoxy polyethylene glycol allyl ether, polypropylene glycol allyl ether, methoxy polypropylene glycol allyl ether, ethoxy polypropylene glycol allyl ether, propoxy polypropylene glycol allyl ether, Polyethylene glycol-2-methylallyl ether, polypropylene glycol-2-methylallyl ether, polyethylene glycol-2-butenyl ether, and polypropylene And at least one selected from glycol-2-butenyl ether and the like.

In another embodiment of the monomer a1, R ^{1 to} R ³ in the formula (I) are hydrogen atoms, R ⁴ is — (CH ₂ ) _r O (AO) _m —Y, and r is 2 In the case, for example, polyethylene glycol-3-butenyl ether, methoxy polyethylene glycol-3-butenyl ether, ethoxy polyethylene glycol-3-butenyl ether, propoxy polyethylene glycol-3-butenyl ether, polypropylene glycol-3-butenyl Ether, methoxy polypropylene glycol-3-butenyl ether, ethoxy polypropylene glycol-3-butenyl ether, propoxy polypropylene glycol-3-butenyl ether, polyethylene glycol-3-methyl-3-butenyl ether, methoxy polyethylene glycol-3 − Tyl-3-butenyl ether, ethoxy polyethylene glycol-3-methyl-3-butenyl ether, propoxy polyethylene glycol-3-methyl-3-butenyl ether, polyproleneglycol-3-methyl-3-butenyl ether, At least one selected from methoxypolypropylene glycol-3-methyl-3-butenyl ether, ethoxypolypropylene glycol-3-methyl-3-butenyl ether, and propoxypolypropylene glycol-3-methyl-3-butenyl ether; One type is mentioned.

<Monomer a2>

In the formula (II), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, R ⁸ represents an alkylene group having 2 to 4 carbon atoms, and M ² represents a hydrogen atom, an alkali It represents a metal, an alkaline earth metal (原子 atom), an organic ammonium group, or an ammonium group.

In the formula (II), R ⁵ , R ⁶ and R ⁷ are each independently at least one selected from a hydrogen atom or a methyl group, and from the viewpoint of improving detergency, R ⁵ and R ⁷ are each a hydrogen atom; R ⁶ is preferably a methyl group. R ⁸ is at least one selected from alkylene groups having 2 to 4 carbon atoms, and from the viewpoint of improving detergency, R ⁸ is preferably an ethylene group, a propylene group, or an isopropylene group, and more preferably an ethylene group. .

In the formula (II), M ² represents a hydrogen atom, an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group. When M ² is a hydrogen atom, the monomer a2 is phosphoric acid. When M ² is an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group, the monomer a2 is a phosphoric acid salt. M ² is preferably a hydrogen atom, an alkali metal, an organic ammonium group, or an ammonium group, more preferably a hydrogen atom, an organic ammonium group, or an ammonium group, and further preferably a hydrogen atom, from the viewpoint of improving the cleaning properties.

In one embodiment of the monomer a2, R ⁵ , R ⁶ and R ⁷ in the formula (II) are a hydrogen atom, R ⁸ is an alkylene group having 2 to 4 carbon atoms, and M ² is a hydrogen atom. In this case, for example, phosphoric acid mono (2-hydroxyethyl) acrylate, phosphoric acid mono (2-hydroxypropyl) acrylate, phosphoric acid mono (2-hydroxyisopropyl) acrylate, and phosphoric acid mono (2-hydroxyethyl) acrylate At least one member selected from the group consisting of (hydroxybutyl) acrylate and the like is preferred, and mono (2-hydroxyethyl) acrylate phosphate is preferred from the viewpoint of improving detergency.

In another embodiment of the monomer a2, R ⁵ and R ⁷ in the formula (II) are a hydrogen atom, R ⁶ is a methyl group, R ⁸ is an alkylene group having 2 to 4 carbon atoms, and M ² Is a hydrogen atom, for example, mono (2-hydroxyethyl) methacrylate phosphate, mono (2-hydroxypropyl) methacrylate phosphate, mono (2-hydroxyisopropyl) methacrylate phosphate, and phosphoric acid At least one selected from mono (2-hydroxybutyl) methacrylic acid esters and the like are mentioned, and mono (2-hydroxyethyl) methacrylic acid phosphate is preferred from the viewpoint of improving the cleaning properties.

<Monomer a3>

In the formula (III), R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, and R ¹² and R ^{13 each} represent an alkylene having 2 to 4 carbon atoms. M ³ represents a hydrogen atom, an alkali metal, an alkaline earth metal (（atom), an organic ammonium group, or an ammonium group.

In the formula (III), R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently at least one selected from a hydrogen atom or a methyl group, and from the viewpoint of improving detergency, R ⁹ , R ¹¹ , R ¹⁵ and R ¹⁶ are preferably a hydrogen atom, and R ¹⁰ and R ¹⁴ are preferably a methyl group. R ¹² and R ¹³ are at least one selected from alkylene groups having 2 to 4 carbon atoms, and from the viewpoint of improving detergency, R ¹² and R ¹³ are preferably an ethylene group, a propylene group, or an isopropylene group, Ethylene groups are more preferred.

In the formula (III), M ³ represents a hydrogen atom, an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group. When M ³ is a hydrogen atom, the monomer a3 is phosphoric acid. When M ³ is an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group, the monomer a3 is a phosphoric acid salt. M ³ is preferably a hydrogen atom, an alkali metal, an organic ammonium group, or an ammonium group, more preferably a hydrogen atom, an organic ammonium group, or an ammonium group, and further preferably a hydrogen atom, from the viewpoint of improving the cleaning properties.

In one embodiment of the monomer a3, R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ in the formula (III) are a hydrogen atom, and R ¹² and R ¹³ have 2 to 4 carbon atoms. When M ³ is a hydrogen atom and is an alkylene group, for example, bis [(2-hydroxyethyl) acrylic acid] ester, bis [(2-hydroxypropyl) acrylic acid] ester, bis [ At least one selected from (2-hydroxyisopropyl) acrylic acid] ester, bis [(2-hydroxybutyl) acrylic acid] ester phosphate, and the like, and from the viewpoint of improving detergency, bisphosphate [(2 -Hydroxyethyl) acrylic acid] ester is preferred.

In another embodiment of the monomer a3, R ⁹ , R ¹¹ , R ¹⁵ and R ¹⁶ in the formula (III) are hydrogen atoms, R ¹⁰ and R ¹⁴ are methyl groups, and R ¹² and R ¹³ have 2 carbon atoms. When the alkylene group is at least 4 and M ³ is a hydrogen atom, for example, bis [(2-hydroxyethyl) methacrylic acid] ester phosphate, bis [(2-hydroxypropyl) methacrylic acid] ester phosphate, At least one selected from bis [(2-hydroxyisopropyl) methacrylic acid] ester phosphate, bis [(2-hydroxybutyl) methacrylic acid] ester phosphate, and the like, from the viewpoint of improving detergency, phosphoric acid Bis [(2-hydroxyethyl) methacrylic acid] ester is preferred.

  The content (molar part) of the structural unit a1 in all the structural units of the component A is preferably 30 mole parts or more based on all the structural units of the component A (100 mole parts), from the viewpoint of improving detergency. It is more preferably at least mol part, more preferably at least 45 mol part, and from the same viewpoint, it is preferably at most 85 mol part, more preferably at most 80 mol part, even more preferably at most 75 mol part. More specifically, the content (mol parts) of the structural unit a1 is preferably from 30 mol parts to 85 mol parts, and more preferably from 40 mol parts to 80 mol parts, based on all the constituent units (100 mol parts) of the component A. Or less, more preferably 45 mol parts or more and 75 mol parts or less.

  The content (mol parts) of the structural unit a2 in all the structural units of the component A is preferably 9 mol parts or more with respect to all the structural units of the component A (100 mol parts) from the viewpoint of improvement in detergency. It is more preferably at least 18 mol parts, more preferably at least 18 mol parts, and from the same viewpoint, it is preferably at most 50 mol parts, more preferably at most 45 mol parts, even more preferably at most 40 mol parts. More specifically, the content (molar part) of the structural unit a2 is preferably from 9 to 50 mole parts, more preferably from 12 to 45 mole parts, based on all the structural units (100 mole parts) of the component A. Or less, more preferably 18 to 40 mol parts.

  The content (molar part) of the structural unit a3 in all the structural units of the component A is preferably 3 mole parts or more based on all the structural units of the component A (100 mole parts) from the viewpoint of improving the detergency. It is more preferably at least 6 mol parts, more preferably at least 6 mol parts, and from the same viewpoint, it is preferably at most 20 mol parts, more preferably at most 17 mol parts, even more preferably at most 15 mol parts. More specifically, the content (mol parts) of the structural unit a3 is preferably from 3 to 20 mol parts, and more preferably from 4 to 17 mol parts, based on all the structural units (100 mol parts) of the component A. Or less, more preferably 6 to 15 mol parts.

  The total content (molar parts) of the constituent units a2 and a3 in all the constituent units of the component A is preferably 12 mole parts or more based on all the constituent units of the component A (100 mole parts) from the viewpoint of improving the detergency. Preferably, it is more preferably at least 16 mol parts, even more preferably at least 24 mol parts, and from the same viewpoint, preferably at most 70 mol parts, more preferably at most 60 mol parts, even more preferably at most 55 mol parts. More specifically, the total content (molar parts) of the constituent units a2 and a3 is preferably from 12 to 70 mole parts, and more preferably 16 mole parts, based on all constituent units (100 mole parts) of the component A. It is more preferably at least 60 mol parts and at most 24 mol parts and at most 55 mol parts.

  The molar ratio [a1 / (a2 + a3)] between the content of the structural unit a1 in all the structural units of the component A and the total content of the structural units a2 and a3 is preferably 0.1 or more from the viewpoint of improving the cleaning properties. , 0.3 or more, more preferably 0.8 or more, and from the same viewpoint, it is preferably 10 or less, more preferably 7 or less, and still more preferably 5 or less. More specifically, the molar ratio [a1 / (a2 + a3)] is preferably 0.1 or more and 10 or less, more preferably 0.3 or more and 7 or less, and even more preferably 0.8 or more and 5 or less.

  The molar ratio (a2 / a3) of the structural unit a2 to the structural unit a3 in all the structural units of the component A is preferably 0.5 or more, more preferably 1 or more, and further preferably 2 or more, from the viewpoint of improving the detergency. Preferably, and from the same viewpoint, 10 or less is preferable, 5 or less is more preferable, and 3 or less is further preferable. More specifically, the molar ratio (a2 / a3) is preferably 0.5 or more and 10 or less, more preferably 1 or more and 5 or less, and even more preferably 2 or more and 3 or less.

  The total content (molar parts) of the constituent units a1, a2, and a3 in all the constituent units of the component A is 80 mole parts with respect to all the constituent units of the component A (100 mole parts) from the viewpoint of improving the detergency. The amount is preferably 90 mol parts or more, more preferably 95 mol parts or more, and from the same viewpoint, 100 mol parts or less is preferable. More specifically, the total content (molar parts) of the structural units a1, a2, and a3 is preferably 80 mole parts or more and 100 mole parts or less, based on all structural units (100 mole parts) of the component A. The molar amount is more preferably from 100 to 100 mol parts, and still more preferably from 95 to 100 mol parts.

  Component A can further contain other structural units other than structural units a1, a2, and a3. Other structural units include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, styrene, ethylene, propylene, vinyl alcohol, allyl alcohol and the like.

  The component A can be obtained by a known method, for example, by polymerizing a monomer mixture containing a monomer a1, a monomer a2, and a monomer a3 by a solution polymerization method. Examples of the solvent used for the solution polymerization include water; aromatic hydrocarbons such as toluene and xylene; alcohols such as ethanol and 2-propanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether; . As the polymerization initiator used for the polymerization, a known radical initiator can be used, and examples thereof include ammonium persulfate. At the time of polymerization, a chain transfer agent can be further used, and examples thereof include thiol-based chain transfer agents such as 2-mercaptoethanol and β-mercaptopropionic acid. In the present disclosure, the content of each structural unit in all the structural units of Component A can be regarded as the ratio of the amount of each monomer used to the total amount of monomers used for polymerization.

  The arrangement of each structural unit constituting the component A may be random, block, or graft.

  The weight average molecular weight of the component A is preferably 8,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, and from the same viewpoint, 150,000 or less from the viewpoint of improving the detergency. Preferably, it is 100,000 or less, more preferably, 50,000 or less. More specifically, the weight average molecular weight of Component A is preferably from 8,000 to 150,000, more preferably from 15,000 to 100,000, even more preferably from 20,000 to 50,000. In the present disclosure, the weight average molecular weight of the component A is based on a gel permeation chromatography method (in terms of polyethylene glycol), and can be specifically measured by the method described in Examples.

  The content of the component A at the time of cleaning the cleaning composition according to the present disclosure is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and 0.02% by mass from the viewpoint of improving cleanability. The above is still more preferred, and the content is more preferably 0.03% by mass or more, and from the viewpoint of improving the cleanability and reducing the wastewater treatment load, the content is preferably 1% by mass or less, more preferably 0.8% by mass or less, and 0.6% by mass or less. It is more preferably at most 0.5% by mass, more preferably at most 0.5% by mass. More specifically, the content of Component A is preferably 0.005% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.8% by mass or less, and 0.02% by mass or more and 0.1% by mass or less. 6% by mass or less is more preferable, and 0.03% by mass or more and 0.5% by mass or less is even more preferable.

[Component B: sulfuric acid]
The cleaning composition according to the present disclosure includes sulfuric acid (component B).

  The content of the component B at the time of cleaning the detergent composition according to the present disclosure is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of improving cleanability, and the same viewpoint. Therefore, it is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less. More specifically, the content of the component B is preferably 0.01% by mass or more and 0.5% by mass or less, more preferably 0.02% by mass or more and 0.3% by mass or less, and 0.02% by mass or more. 0.2 mass% or less is still more preferable, and 0.02 mass% or more and 0.1 mass% or less are still more preferable.

  The mass ratio of the component A to the component B (the content of the component A / the content of the component B) in the detergent composition according to the present disclosure is preferably 0.1 or more, from the viewpoint of improving the detergency. 5 or more is more preferable, 1.0 or more is still more preferable, 1.5 or more is still more preferable, and from the same viewpoint, 20 or less is preferable, 15 or less is more preferable, 12 or less is further preferable, and 10 or less is preferable. Even more preferred. More specifically, the mass ratio between component A and component B is preferably 0.1 or more and 20 or less, more preferably 0.5 or more and 15 or less, still more preferably 1.0 or more and 12 or less, and 1.5 or more. More preferably, it is 10 or less.

[Component C: water]
As the water of the component C contained in the detergent composition according to the present disclosure, ion-exchanged water, RO water, distilled water, pure water, and ultrapure water can be used. The content of the component C may be appropriately set according to the usage of the cleaning composition according to the present disclosure.

  The content of the component C at the time of cleaning of the cleaning composition according to the present disclosure is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 97% by mass or more, from the viewpoint of improving detergency. And more preferably at least 99.9% by mass, and more preferably at most 99.85% by mass, from the same viewpoint. More specifically, the content of the component C at the time of washing is preferably 90% by mass to 99.9% by mass, more preferably 95% by mass to 99.85% by mass, and 97% by mass to 99.85%. % By mass or less, more preferably 98% by mass or more and 99.85% by mass or less.

[Component D: reducing agent]
The cleaning composition according to the present disclosure can further include a reducing agent (component D) in one or more embodiments.

  Component D may be any component having a reducing property under acidic conditions, and examples thereof include thiourea, ascorbic acid, isoascorbic acid, hydrogen peroxide, and sulfites (eg, sodium sulfite, ammonium sulfite, sodium hyposulfite, Sodium thiosulfate (eg, sodium thiosulfate, ammonium thiosulfate, etc.), aldehyde (eg, formaldehyde, acetaldehyde, etc.), phosphorus-based reducing agent (eg, tris-2-carboxyethylphosphine, etc.), amine-based Reducing agents (eg, hydroxylamine, diethylhydroxylamine, tryptophan, histidine, methionine, phenylalanine, etc.), phenolic reducing agents (eg, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 2,4-benzenetriol, dibutylhydroxytoluene, etc.), 1,4-naphthoquinone-2-sulfonic acid, gallic acid and derivatives thereof, and the like, and these can be used alone or in combination of two or more. . From the viewpoint of improving the detergency, at least one of thiourea and ascorbic acid is preferred. The ascorbic acid includes, for example, one or more selected from L-ascorbic acid, erythorbic acid and salts thereof, and preferably one or more selected from L-ascorbic acid and salts thereof from the viewpoint of improving detergency. And L-ascorbic acid are more preferred.

  The content of the component D at the time of cleaning of the cleaning composition according to the present disclosure is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and 0.004% by mass, from the viewpoint of improving cleanability. The above is still more preferable, and from the same viewpoint, 1% by mass or less is preferable, 0.5% by mass or less is more preferable, and 0.2% by mass or less is further preferable. More specifically, the content of the component D is preferably from 0.001% by mass to 1% by mass, more preferably from 0.002% by mass to 0.5% by mass, and more preferably from 0.004% by mass to 0.5% by mass. The content is more preferably 2% by mass or less.

  The mass ratio of the component A to the component D (the content of the component A / the content of the component D) in the detergent composition according to the present disclosure is preferably 0.05 or more from the viewpoint of improving detergency. 1 or more is more preferable, 0.2 or more is more preferable, and from the same viewpoint, 5 or less is preferable, 4 or less is more preferable, and 3 or less is further more preferable. More specifically, the mass ratio of component A to component D is preferably 0.05 or more and 5 or less, more preferably 0.1 or more and 4 or less, and even more preferably 0.2 or more and 3 or less.

[Other ingredients]
The cleaning composition according to the present disclosure may contain other components as necessary in addition to the components A to D. Other components include polymers other than component A, acids other than component B, chelating agents (for example, aminocarboxylic acids such as hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, and ethylenediaminetetraacetic acid), solubilizing agents, and preservatives. Rust inhibitors, bactericides, antibacterial agents, silicone-based defoamers, antioxidants, esters (eg, coconut fatty acid methyl and benzyl acetate), alcohols and the like. The content of other components during cleaning of the cleaning composition according to the present disclosure is preferably 0% by mass or more and 2% by mass or less, and 0% by mass or more and 1.5% by mass from the viewpoint of not impairing the effects of the present disclosure. The following is more preferable, 0 mass% or more and 1.3 mass% or less is further preferable, and 0 mass% or more and 1 mass% or less is still more preferable.

[PH of detergent composition]
The pH at the time of cleaning the cleaning composition according to the present disclosure is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, and still more preferably 2.5 or less, from the viewpoint of improving the detergency. One or more is preferred. More specifically, the cleaning pH of the cleaning composition according to the present disclosure is preferably 1 to 5 or less, more preferably 1 to 4 or less, still more preferably 1 to 3 or less, and 1 to 2.5 or less. Is even more preferred.

  Adjustment of the pH of the cleaning composition according to the present disclosure can be performed using Component B (sulfuric acid). For example, inorganic acids such as nitric acid; oxycarboxylic acids, polycarboxylic acids, aminopolycarboxylic acids, The reaction can also be performed using an organic acid such as an amino acid; and a basic substance such as a metal salt or an ammonium salt thereof, ammonia, sodium hydroxide, potassium hydroxide, or an amine.

  In the present disclosure, the “pH at the time of washing” is the pH at the time of use (after dilution) of the detergent composition at 25 ° C., and can be measured using a pH meter. Specifically, it can be measured by the method described in Examples.

[Method for producing detergent composition]
The cleaning composition according to the present disclosure can be produced, for example, by blending the components A to C, and if necessary, the component D and other components by a known method. For example, the cleaning composition according to the present disclosure can be obtained by blending at least the components A to C. Therefore, the present disclosure relates in one aspect to a method for producing a cleaning composition, which comprises at least a step of blending the components A to C. In the present disclosure, "compounding" includes mixing components A to C and, if necessary, component D and other components simultaneously or in any order. In the method for producing a cleaning composition according to the present disclosure, the amount of each component may be the same as the content of each component of the above-described cleaning composition according to the present disclosure.

  In the present disclosure, “the content of each component at the time of cleaning the cleaning composition” is used in one or a plurality of embodiments in a cleaning step, that is, a time point when use for cleaning is started (when used). Means the content of each component of the cleaning composition.

  The detergent composition according to the present disclosure may be prepared as a concentrate in which the amount of water of the component C is reduced as long as separation and precipitation do not occur and storage stability is not impaired. The concentrate of the detergent composition is preferably a concentrate having a dilution factor of 10 or more from the viewpoint of transportation and storage, and is preferably a concentrate having a dilution ratio of 100 or less from the viewpoint of storage stability. . The concentrate of the detergent composition can be used after being diluted with water so that each component has the above-mentioned content (that is, the content at the time of washing) at the time of use. Furthermore, the concentrate of the detergent composition can be used by adding each component separately at the time of use. In the present disclosure, “when using” or “when washing” the concentrate of the detergent composition refers to a state in which the concentrate of the detergent composition is diluted.

  The pH of the concentrate of the cleaning composition according to the present disclosure is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, and still more preferably 2.5 or less, from the viewpoint of improving the washing properties after dilution. . In the present disclosure, the pH of the concentrate of the detergent composition can be measured by the same method as the above-described pH at the time of washing.

[Substrate to be cleaned]
In one or a plurality of embodiments, the cleaning composition according to the present disclosure uses a polishing liquid composition containing ceria and silica for cleaning a substrate after polishing using a polishing liquid composition containing ceria (ceria slurry). Cleaning of the substrate after polishing, cleaning of the substrate after CMP using ceria slurry, cleaning of the substrate after CMP using a polishing composition containing ceria and silica, foreign matter derived from ceria abrasive grains adhered to the substrate surface It can be used for cleaning a substrate that has been cleaned, or for cleaning a substrate having foreign matter derived from ceria and silica abrasive particles adhered to the substrate surface. The cleaning composition according to the present disclosure can be used for substrates to be cleaned of various materials and shapes.
Examples of the substrate to be cleaned include, for example, a substrate after polishing, specifically, a substrate after polishing using a polishing composition containing ceria, and a substrate after polishing using a polishing composition containing ceria and silica. Substrate, a substrate after CMP using a polishing composition containing ceria, a substrate after CMP using a polishing composition containing ceria and silica, a substrate having foreign substances derived from ceria abrasive grains adhered to the substrate surface, or And a substrate having a foreign material derived from ceria and silica abrasive particles adhered to the substrate surface. Examples of the substrate include substrates for semiconductor devices such as a silicon substrate, a glass substrate, and a ceramic substrate. Accordingly, the present disclosure, in another aspect, relates to the use of the cleaning composition according to the present disclosure for cleaning a substrate for a semiconductor device.

  The surface material of the substrate to be cleaned is not particularly limited. For example, single-crystal silicon, polycrystalline silicon, amorphous silicon, thermal silicon oxide film, undoped silicate glass film, phosphorus-doped silicate glass film, boron-doped silicate glass film, phosphorus-doped Examples thereof include a silicate glass film, a tetraethylorthosilicate (TEOS) film, a plasma CVD oxide film, a silicon nitride film, a silicon carbide film, a silicon oxide carbide film, and a silicon oxide carbide nitride film. Further, glass, quartz, quartz, ceramics, and the like can also be used. In one or more embodiments, the substrate to be cleaned may be a substrate composed of these materials alone, a substrate patterned with a certain distribution of two or more materials, or a laminated substrate.

[Substrate cleaning method]
The present disclosure includes, in one embodiment, a step of cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure, wherein the substrate to be cleaned is a substrate used for manufacturing a substrate for a semiconductor device. (Hereinafter, also referred to as “cleaning method according to the present disclosure”). The above-described substrate can be used as the substrate to be cleaned. In one or more embodiments, the cleaning step may include a step of bringing the cleaning composition according to the present disclosure into contact with a substrate to be cleaned. Examples of a method for cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure include, for example, a method of immersing the substrate in a cleaning bath and a method of bringing the substrate into contact in a bath of an ultrasonic cleaning apparatus, and a method of cleaning the cleaning composition. A method of injecting and contacting in a spray form, a method of discharging or spraying a cleaning composition on a rotating substrate to be cleaned, a method of contacting by spraying, and applying a ultrasonic wave to the cleaning composition to form a spray. Examples include a method of injecting and contacting, and a method of contacting via a brush or the like while spraying a detergent composition.

  When the cleaning composition according to the present disclosure is a concentrate, the cleaning method according to the present disclosure may further include a dilution step of diluting the concentrate of the cleaning composition. The cleaning method according to the present disclosure preferably includes a step of bringing the substrate to be cleaned into contact with the cleaning composition, rinsing with water, and drying. According to the cleaning method of the present disclosure, ceria remaining on the substrate surface can be efficiently removed. From the viewpoint of cleanability by the cleaning method according to the present disclosure, it is preferable to use a polishing composition containing ceria or a polishing composition containing ceria and silica for CMP. In the cleaning method according to the present disclosure, it is preferable that the cleaning composition according to the present disclosure is easily irradiated with ultrasonic waves at the time of contact between the cleaning composition and the substrate to be cleaned because the cleaning power is easily exerted. More preferably, the ultrasonic waves are relatively strong. Ultrasonic irradiation conditions are preferably from 20 to 2,000 kHz, more preferably from 40 to 2,000 kHz, and still more preferably from 40 to 1,500 kHz, from the same viewpoint.

[Method for Manufacturing Substrate for Semiconductor Device]
The present disclosure, in one aspect, includes a method of manufacturing a substrate for a semiconductor device (hereinafter, “a method of manufacturing a substrate according to the present disclosure”) including a cleaning step of cleaning a substrate to be cleaned using the cleaning composition according to the present disclosure. Also referred to). The above-described substrate can be used as the substrate to be cleaned. The cleaning method and the cleaning conditions in the cleaning step of the substrate manufacturing method according to the present disclosure can be the same as those in the above-described cleaning method according to the present disclosure.

  In one embodiment, a substrate manufacturing method according to the present disclosure includes a step of performing CMP using a polishing liquid composition (ceria slurry) containing ceria performed in a step of forming an element isolation structure, and a cleaning agent according to the present disclosure. The method may include a step of cleaning the substrate to be cleaned using the composition.

The substrate manufacturing method according to the present disclosure may include the following steps 1 and 2 in other embodiments.
Step 1: Polishing the substrate using the polishing composition containing ceria Step 2: Cleaning the substrate polished in Step 1 using the cleaning composition according to the present disclosure

Here, a specific example of the step of performing CMP will be described below.
First, a silicon substrate including a silicon dioxide layer is formed by exposing the silicon substrate to oxygen in an oxidation furnace. Next, a silicon nitride (Si ₃ N ₄ ) film is formed on the silicon dioxide layer side of the silicon substrate, for example, on the silicon dioxide layer by, for example, a CVD method (chemical vapor deposition). Next, a substrate including the thus obtained silicon substrate and a silicon nitride film disposed on one main surface side of the silicon substrate, for example, disposed on one main surface of the silicon substrate and the silicon substrate A silicon nitride film or a silicon nitride film disposed on one main surface of a silicon substrate, the silicon nitride film is passed through the silicon nitride film using photolithography technology, and the trench bottom is made of silicon. A trench reaching the substrate is formed. Next, a silicon oxide (SiO ₂ ) film for filling the trench is formed by, for example, a CVD method using a silane gas and an oxygen gas, the silicon oxide is buried in the trench, and the trench and the silicon nitride film are covered with the silicon oxide film. The substrate to be polished is obtained. Due to the formation of the silicon oxide film, the trench is filled with silicon oxide of the silicon oxide film, and the surface of the silicon nitride film opposite to the surface on the silicon substrate side is covered with the silicon oxide film. The surface of the silicon oxide film thus formed opposite to the surface on the silicon substrate side has a step formed corresponding to the unevenness of the lower layer. Next, by a CMP method, the silicon oxide film is polished with ceria slurry until at least the surface opposite to the surface of the silicon nitride film on the silicon substrate side is exposed. More preferably, the surface of the silicon oxide film and the surface of the silicon nitride film are removed. The silicon oxide film is polished until the surface is flush.

  In the substrate manufacturing method according to the present disclosure, by using the cleaning composition according to the present disclosure for cleaning a substrate to be cleaned, foreign substances such as abrasive grains and polishing debris remaining on the substrate surface after CMP are reduced, and foreign substances are reduced. Since the occurrence of defects in the post-process due to the residual is suppressed, a highly reliable semiconductor device substrate can be manufactured. Further, by performing the cleaning method according to the present disclosure, it becomes easy to clean residues such as abrasive grains and polishing debris on the substrate surface after CMP, so that the cleaning time can be reduced, and the manufacturing efficiency of the semiconductor device substrate can be reduced. Can be improved.

[kit]
The present disclosure relates in one aspect to a kit for use in the cleaning method according to the present disclosure and / or the substrate manufacturing method according to the present disclosure. One embodiment of the kit according to the present disclosure includes, for example, a solution containing component A (first solution) and a solution containing component B (second solution) in a state where they are not mixed with each other. And a kit in which these are mixed at the time of use (two-pack detergent composition). The above-mentioned component D and other components may be mixed in each of the first liquid and the second liquid as needed. At least one of the first liquid and the second liquid may contain part or all of the component C (water). After the first liquid and the second liquid are mixed, they may be diluted with component C (water) as necessary.

  Hereinafter, the present disclosure will be specifically described with reference to examples, but the present disclosure is not limited to these examples.

1. Preparation of Polymer (Component A) In preparing polymers A1 to A3 shown in Table 1, the following monomers were used.
<Monomer a1-1>
Methoxy polyethylene glycol monomethacrylic acid ester [EO average addition mole number 23, manufactured by Shin-Nakamura Chemical Co., Ltd., M-230G] [When represented by the formula (I), R ¹ , R ³ = hydrogen atom, R ² = CH ₃ , _{^{R 4 = - (CH 2)}} qCOO (EO) n-X (q = 0, n = 23, X = CH 3)]
<Monomer a1-2>
Methoxypolyethylene glycol monomethacrylate [average number of moles of added EO: 9, manufactured by Shin-Nakamura Chemical Co., Ltd., M-90G] [When represented by the formula (I), R ¹ , R ³ = hydrogen atom, R ² = CH ₃ , _{^{R 4 = - (CH 2)}} qCOO (EO) n-X (q = 0, n = 9, X = CH 3)]
<Monomer a1-3>
1000 parts by mass of polyethylene glycol monomethyl ether (weight average molecular weight: 5344) having an ethylene oxide addition mole number of 120 and melted at 80 ° C. are charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a cooling condenser. It is. Next, 3 parts by mass of hydroquinone and 32 parts by mass of p-toluenesulfonic acid were added. Here, air was introduced into the reaction solution at a flow rate of 6 mL / min per kg of the total mass of polyethylene glycol monomethyl ether and methacrylic acid, and nitrogen was introduced into the gas phase of the reaction vessel at a flow rate of 12 mL / min. 483 parts by mass of methacrylic acid (an amount that is 30 mol times the amount of polyethylene glycol monomethyl ether) were charged, and heating and depressurization in the reaction vessel were started. The pressure was controlled at 26.7 kPa, and the time when the temperature of the reaction solution reached 105 ° C. was defined as the reaction start time. The reaction was continued while heating to maintain the temperature of the reaction solution at 110 ° C. while distilling out the reaction water and methacrylic acid. Was done. The pressure was reduced to 12 to 13.3 kPa one hour after the start of the reaction, and was maintained as it was. Six hours after the start of the reaction, the pressure was returned to normal pressure, neutralized by adding 1.05 times equivalent of a 48% aqueous sodium hydroxide solution to p-toluenesulfonic acid, and the reaction was terminated. Thereafter, the temperature of the reaction solution was maintained at 130 ° C. or lower, and unreacted methacrylic acid was recovered by a vacuum distillation method to obtain an esterification reaction product. After cooling to 100 ° C., 200 parts by mass of saturated saline and 1000 parts by mass of toluene were added to the reaction product, and the mixture was adjusted to 50 ° C. The extraction of the separated lower layer, the addition of 200 parts by mass of a saturated saline solution, and the separation were repeated 5 times, then, toluene was distilled off, and purified methoxypolyethylene glycol monomethacrylate (average number of moles of added EO of 120) was obtained. , Monomer a1-3) [R ¹ , R ³ = hydrogen atom, R ² = CH ₃ , R ⁴ = − (CH ₂ ) qCOO (EO) n−X (q = 0, n = 120, X = CH ₃ )].
<Monomer a2-1>
Mono (2-hydroxyethyl) methacrylate phosphate [expressed by the formula (II), R ⁵ , R ⁷ = hydrogen atom, R ⁶ = CH ₃ , R ⁸ = ethylene group, M ² = hydrogen atom]
<Monomer a3-1>
Bis [(2-hydroxyethyl) methacrylic acid] ester [expressed by the formula (III), R ⁹ , R ¹¹ , R ¹⁵ , R ¹⁶ = hydrogen atom, R ¹⁰ , R ¹⁴ = CH ₃ , R ¹² , R ¹³ = ethylene group, M ³ : hydrogen atom]

<Production Example of Polymer A1>
726.3 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C in a nitrogen atmosphere. A mixture of 28.2 g of a mixture of 130.0 g of monomer a1-1, monomer a2-1 and monomer a3-1 (manufactured by Unichemical Co., Phosmer M) and 3.35 g of mercaptopropionic acid, and ammonium persulfate 5 A solution obtained by dissolving 0.0 g in 45.0 g of water was added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 2.5 g of ammonium persulfate in 15.0 g of water was added dropwise over 30 minutes, followed by aging at the same temperature (80 ° C.) for 1.5 hours. After completion of the aging, the mixture was neutralized with a 20% aqueous sodium hydroxide solution to obtain a copolymer (polymer A1) having a weight average molecular weight of 43,000.

<Production Example of Polymer A2>
726.3 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C in a nitrogen atmosphere. A mixture of 28.2 g of a mixture of 150.0 g of monomer a1-2, monomer a2-1 and monomer a3-1 (manufactured by Unichemical Co., Phosmer M) and 5.34 g of 3-mercaptopropionic acid; A solution obtained by dissolving 9.2 g of ammonium sulfate in 45.0 g of water was added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 4.6 g of ammonium persulfate in 15.0 g of water was added dropwise over 30 minutes, followed by aging for 1.5 hours at the same temperature (80 ° C.). After completion of the aging, the mixture was neutralized with a 20% sodium hydroxide solution to obtain a copolymer having a weight average molecular weight of 27,000 (polymer A2).

<Production Example of Polymer A3>
317.0 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. A mixture of 323.0 g of monomer a1-3, 46.5 g of methacrylic acid and 239.0 g of water mixed and dissolved, and a mixture of 1.90 g of 2-mercaptoethanol and 4.17 g of ammonium persulfate dissolved in 37.53 g of water For 2 hours. A solution prepared by dissolving 1.39 g of ammonium persulfate in 12.51 g of water was added dropwise over 30 minutes, and then aged at the same temperature (75 ° C.) for 1 hour. After completion of aging, the mixture was neutralized with a 48% sodium hydroxide solution to obtain a copolymer having a weight average molecular weight of 39000 (polymer A3).

[Measurement of weight average molecular weight]
The weight average molecular weight of each polymer used was measured under the following conditions using a gel permeation chromatography (hereinafter also referred to as “GPC”) method. Table 1 shows the measurement results.
<GPC conditions>
Column: G4000PWXL + G2500PWXL (Tosoh Corporation)
Eluent: 0.2 M phosphate buffer / CH ₃ CN = 9/1 (volume ratio)
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample concentration: 0.5mg / mL
Standard substance: polyethylene glycol equivalent

2. Preparation of detergent composition (Examples 1 to 6 and Comparative Examples 1 to 4)
The components were weighed in a 100 mL glass beaker so as to have the contents shown in Table 2, and mixed under the following conditions to prepare the detergent compositions of Examples 1 to 6 and Comparative Examples 1 to 4. The numerical values of each component in Table 2 are mass% unless otherwise noted, and are shown as effective components. The pH in Table 2 is the pH of the cleaning composition at 25 ° C., measured using a pH meter (manufactured by Toa DKK Ltd., HM-30G), and immersed in the cleaning composition for 1 minute. It is the numerical value after.
<Mixing conditions>
Liquid temperature: 25 ° C
Stirrer: Magnetic stirrer (50mm rotor)
Rotation speed: 300 rpm
Stirring time: 10 minutes

In the preparation of the cleaning compositions shown in Table 2, the following components were used as the components B, C and D.
Sulfuric acid [Fuji Film Wako Pure Chemical Industries, Ltd., high-purity special grade] (Component B)
Water [Ultra pure water produced using a continuous pure water production system (Pure Conti PC-2000VRL type) and subsystem (McAce KC-05H type) manufactured by Kurita Water Industries Ltd.] (Component C)
Ascorbic acid [L (+)-ascorbic acid (special grade) manufactured by Kanto Chemical Co., Ltd.] (Component D)
Thiourea [Nakarai Tesque Co., Ltd., JIS reagent special grade] (Component D)

3. Preparation of test piece Amorphous ceria (fired and crushed ceria GPL-C1010, manufactured by Showa Denko KK) and ammonium polyacrylate (weight average molecular weight 21,000) were mixed in water. A polishing composition of 4% by mass was prepared. As a test piece before polishing, a silicon oxide film test piece cut out to a size of 40 mm × 40 mm from a silicon oxide film having a thickness of 2000 nm formed on one surface of a silicon wafer by a TEOS-plasma CVD method was used. Further, "MA-300" manufactured by Musashino Electronics Co., Ltd. having a platen diameter of 300 mm was used as a polishing apparatus, and a laminated pad "IC1000 / SUBA400" manufactured by Nitta Haas Co., Ltd. was used as a polishing pad. Affixing the polishing pad to the surface plate of the polishing apparatus, setting the test piece in the holder, so that the surface on which the silicon oxide film of the test piece was formed is downward, that is, such that the silicon oxide film is in contact with the polishing pad, The holder was placed on the polishing pad. Further, the weight was placed on the holder so that the load applied to the test piece was 300 g weight / cm ^2, and the polishing composition was dropped at a rate of 50 mL / min onto the center of the platen on which the polishing pad was attached. The silicon oxide film test piece was polished by rotating each of the platen and the holder in the same rotation direction at 90 rotations / minute for 1 minute to prepare a test piece for cleaning evaluation.

4. Evaluation of Cleaning Composition The following evaluation was performed using the prepared cleaning compositions of Examples 1 to 6 and Comparative Examples 1 to 4.
The test piece for cleaning evaluation was immersed in the detergent composition for 60 seconds, rinsed with running water, dried, and then the surface of the test piece was observed with "Desktop microscope Miniscope TM3030" manufactured by Hitachi Technologies, Ltd. The number of residual ceria abrasive grains that could be confirmed in an observation field of 10,000 times was counted. In Table 2, it is shown that the smaller the number, the better the cleaning property.

  As shown in Table 2, the cleaning compositions of Examples 1 to 6 were superior to the cleaning compositions of Comparative Examples 1 to 4 in detergency against ceria.

  The cleaning composition of the present disclosure is useful as a cleaning composition used in a manufacturing process of a substrate for a semiconductor device, shortening the cleaning process of a substrate to which ceria is attached, and improving the performance and performance of the manufactured semiconductor device substrate. The reliability can be improved, and the productivity of the semiconductor device can be improved.

Claims (10)

A monomer a1 represented by the following formula (I) or a structural unit a1 derived from an anhydride thereof, a structural unit a2 derived from a monomer a2 represented by the following formula (II), and a monomer a3 represented by the following formula (III) A cleaning composition for a substrate for a semiconductor device, comprising a polymer (component A) containing the structural unit a3, sulfuric acid (component B), and water (component C).

[In the formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group, or — (CH ₂ ) _p COOM ¹ , and R ⁴ represents — (CH ₂ ) _q COO ( AO) _n -X or-(CH ₂ ) _r O (AO) _m -Y, and M ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or ammonium P, q and r each independently represent an integer of 0 or more and 2 or less; AO represents an alkyleneoxy group having 2 or 3 carbon atoms; n and m each independently represent an average addition mole of AO X and Y each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

[In the formula (II), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, R ⁸ represents an alkylene group having 2 to 4 carbon atoms, M ² represents a hydrogen atom, It represents an alkali metal, an alkaline earth metal (原子 atom), an organic ammonium group, or an ammonium group. ]

[In the formula (III), R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, and R ¹² and R ^{13 each} have 2 to 4 carbon atoms. M ³ represents a hydrogen atom, an alkali metal, an alkaline earth metal (１ ／ atom), an organic ammonium group, or an ammonium group. ]   The cleaning composition according to claim 1, wherein the weight average molecular weight of Component A is from 8,000 to 150,000.   The molar ratio [a1 / (a2 + a3)] between the content of the structural unit a1 in all the structural units of the component A and the total content of the structural units a2 and a3 is 0.1 or more and 10 or less. 3. The cleaning composition according to item 1.   The cleaning composition according to any one of claims 1 to 3, wherein the mass ratio of component A to component B (content of component A / content of component B) is 0.1 or more and 20 or less.   The cleaning composition according to any one of claims 1 to 4, which has a pH of 5 or less when used.   The cleaning composition according to any one of claims 1 to 5, further comprising a reducing agent (Component D).   A step of cleaning a substrate to be cleaned using the cleaning composition according to any one of claims 1 to 6, wherein the substrate to be cleaned is a substrate used for manufacturing a substrate for a semiconductor device. Cleaning method.   The method for cleaning a substrate according to claim 7, wherein the substrate to be cleaned is a substrate polished using a polishing composition containing ceria.   A method for manufacturing a substrate for a semiconductor device, comprising a step of cleaning a substrate to be cleaned using the cleaning composition according to any one of claims 1 to 6.   The method for manufacturing a substrate for a semiconductor device according to claim 9, wherein the substrate to be cleaned is a substrate polished using a polishing composition containing ceria.